JPH0321541B2 - - Google Patents

Abstract

An alkali metal or an alkaline earth metal salt of an acyloxybenzenesulfonate of the formula:in which R is a hydrocarbyl group containing up to 30 carbon atomsselected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl and M is an alkali metal or an alkaline earth metal is prepared by reacting at elevated temperature the corresponding hydroxybenzene sulfonate salt of the formula:with an aryl ester of the formula:in which R is as defined above.

Description

[Detailed description of the invention]

The present invention relates to a process for making certain alkali metal and alkaline earth metal salts of acyloxybenzene sulfonates, and more particularly to a process for making these salts by reaction between the corresponding salts of hydroxybenzene sulfonic acids and aryl esters. The acyloxybenzene sulfonate salts of the present invention have many uses. For example, they are used in the textile industry as activators for peroxide bleaching of textiles and as dyeing aids in the dyeing of acrylic fibers. In a particular embodiment, and by way of illustration, the invention provides the following equation: It is contemplated to produce sodium 4-nonanoyloxybenzenesulfonate according to the following. In another embodiment, the invention provides the formula: of acyloxybenzene sulfonates in which R is a hydrocarbyl group containing up to 30 carbon atoms and is selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl and M is an alkali metal or alkaline earth metal. Corresponding formulas for alkali metal and alkaline earth metal salts at elevated temperatures; Hydroxybenzene sulfonate salt and formula: (wherein R and M are as defined above)
It is contemplated that the product can be produced by reacting with an aryl ester of The aryl esters of this invention are known in the art, as are the methods for their preparation.
For example, US Pat. The synthesis of aryl esters of the formula acyl OR (where R represents the aryl group attached to the phenolic hydroxyl in the phenol) by heating in the presence of phenol is disclosed. Aslony, “Direct Esterification of Phenols with Higher Fatty Acids,” Journal of the American
Chemists'Society, 32, 170-172 (1955) is 115-
A large number of monohydric phenols by direct esterification of phenols and higher fatty acids, optionally in the presence of catalysts such as sulfuric acid, phosphoric acid, zinc stearate, lead stearate and triphenyl phosphite, at reaction temperatures between 290°C. and a method for producing fatty acid esters of dihydric phenols. Hydroxybenzenesulfonate salts that can be used according to the invention have the formula: (M in the formula is an alkali metal or alkaline earth metal). The metal sulfonate functionality can be attached to any aromatic carbon atom ortho, meta, or para to the hydroxyl group in the ring. The hydroxybenzenesulfonate salts of the present invention are known compounds and
“Sulfonation and nitrification reactions promoted by boron fluoride” by RJThomas et al.
Industrial and Engineering Chemistry.32, 408
-410 (1940), by methods known in the art, such as treating phenols with sulfuric acid in the presence of boron fluoride at elevated temperatures. Good examples of hydroxybenzenesulfonate salt reactants are: sodium 2-hydroxybenzenesulfonate; sodium 3-hydroxybenzenesulfonate; sodium 4-hydroxybenzenesulfonate; potassium 2-hydroxybenzenesulfonate; potassium 3-hydroxybenzenesulfonate; Potassium 4-hydroxybenzenesulfonate; Calcium 2-hydroxybenzenesulfonate; Calcium 3-hydroxybenzenesulfonate; Calcium 4-hydroxybenzenesulfonate; Preferred examples of acyl ester reactants that can be used in the present invention are: phenyl formate; phenyl acetate; phenyl propionate; phenyl butanoate; phenyl pentanoate; phenyl hexanoate; phenyl heptanoate; phenyl octoate; Phenyl nonanoate; phenyl decanoate; phenyl undecanoate; phenyl dodecanoate; phenyl tridecanoate; phenyl nonadecanoate; phenyl eicosanoate; phenyl tricontanoate; phenyl acrylate; 2: phenyl butenoate; phenyl 2-pentenoate; 5 -phenyl hexenoate; phenyl 4-heptenoate; phenyl 3-octenoate; phenyl 4-decanoate; phenyl 2-undecanoate; phenyl 3-dodecanoate; phenyl 2-octadecenoate; phenyl 2-eicosenoate; 3-tetracosene phenyl acid; phenyl 2-hexacosenate; phenyl 2-triacontenoate; phenyl benzoate; phenyl acetate; phenyl propionate; phenyl butanoate; phenyl pentanoate; phenyl phenylhexanoate; phenyl decanoate; phenyl undecanoate; phenyl dodecanoate; phenyl heptadecanoate; phenyl octadecanoate; phenyl naphthoate; phenyl cyclobutanecarboxylate; phenyl cyclopentanecarboxylate; phenyl cyclohexanecarboxylate; Phenyl dodecanecarboxylate; Phenyl cycloheptadecanecarboxylate; Phenyl cycloeicosancarboxylate; Phenyl 2-methylbenzoate; Phenyl 3-ethylbenzoate; Phenyl 2,3-dimethylbenzoate; Phenyl 2-propylbenzoate; Phenyl -isopropylbenzoate; Phenyl 2- t -butylbenzoate; Phenyl 4-octylbenzoate; Phenyl 4-decylbenzoate; Phenyl 4-dodecylbenzoate; Phenyl 4-pentadecylbenzoate; Phenyl 4-octadecylbenzoate; mixtures thereof and the like. Good examples of acyloxybenzenesulfonate salt products of this method are: Sodium 2-methanoyloxybenzenesulfonate; Sodium 3-methanoyloxybenzenesulfonate; Sodium 4-methanoyloxybenzenesulfonate; Sodium 2-ethanoyl Oxybenzenesulfonate; Potassium 3-ethanoyloxybenzenesulfonate; Calcium 4-ethanoyloxybenzenesulfonate; Sodium 2-propanoyloxybenzenesulfonate; Potassium 3-propanoyloxybenzenesulfonate; Calcium 4-propanoyloxybenzenesulfonate; Sodium 4-Pentanoyloxybenzenesulfonate; Sodium 4-hexanoyloxybenzenesulfonate; Calcium 2-heptanoyloxybenzenesulfonate; Potassium 3-heptanoyloxybenzenesulfonate; Sodium 4-heptanoyloxybenzenesulfonate; Sodium 4-octanoyloxy Benzene sulfonate; Potassium 3-nonanoyloxybenzenesulfonate; Sodium 4-nonanoyloxybenzenesulfonate; Sodium 4-decanoyloxybenzenesulfonate; Sodium 4-undecanoyloxybenzenesulfonate; Sodium 4-pentadecanoyloxybenzenesulfonate; Sodium 4-icosanoyloxybenzenesulfonate; Sodium 4-hexacosonoyloxybenzenesulfonate; Sodium 4-triacontanoyloxybenzenesulfonate; Sodium 4-acryloyloxybenzenesulfonate; Sodium 4-(butyl-2-enoyloxy)
Benzene sulfonate; Sodium 4-(pentyl-2-enoyloxy)benzenesulfonate; Sodium 4-(hexyl-2-enoyloxy)benzenesulfonate; Sodium 4-(heptyl-3-enoyloxy)benzenesulfonate; Sodium 4-(octyl-4- enoyloxy)benzenesulfonate; sodium 4-(nonyl-2-enoyloxy)
Benzene sulfonate; sodium 4-(decyl-2-enoyloxy)
Benzene sulfonate; Sodium 4-(hexadecyl-4-enoyloxy)benzenesulfonate; Sodium 4-(heptadecyl-2-enoyloxy)benzenesulfonate; Sodium 4-(nonadecyl-4-enoyloxy)benzenesulfonate; Sodium 4-(icosyl-2- Sodium 4-(tricosyl-4-enoyloxy)benzenesulfonate; Sodium 4-(heptacyl-3-enoyloxy)benzenesulfonate; Sodium 4-(triacontyl-2-enoyloxy)benzenesulfonate; Sodium 4-benzoyloxybenzene Sulfonates; Sodium 4-phenylacetoyloxybenzenesulfonate; Calcium 4-phenylacetoyloxybenzenesulfonate; Potassium 4-phenylpropanoyloxybenzenesulfonate; Sodium 4-(phenylbutanoyloxybenzenesulfonate); Phenylpentanoyloxybenzenesulfonate; Sodium 4-phenylheptanoyloxybenzenesulfonate; Sodium 4-phenyloctanoyloxybenzenesulfonate; Sodium 4-phenyldecanoyloxybenzenesulfonate; Sodium 4-phenyldodecanoyloxybenzene Sulfonates; Sodium 4-phenylheptadecanoyloxybenzenesulfonate; Sodium 4-phenyl octadecanoyloxybenzenesulfonate; Sodium 4-naphthoyloxybenzenesulfonate; Sodium 4-cyclobutylmethanoyloxybenzenesulfonate; Sodium 4-cyclopentyl Methanoyloxybenzenesulfonate; Sodium 4-cyclohexylmethanoyloxybenzenesulfonate; Sodium 4-cycloheptylmethanoyloxybenzenesulfonate; Sodium 4-cycloheptyldecanoyloxybenzenesulfonate; Sodium 4-(2-methylbenzoyloxy)
Benzene sulfonate; sodium 4-(3-ethylbenzoyloxy)
Benzene sulfonate; Sodium 4-(2,3-dimethylbenzoyloxy)benzenesulfonate; Sodium 4-(2-propylbenzoyloxy)benzenesulfonate; Sodium 4-(2-isopropylbenzoyloxy)benzenesulfonate; Sodium 4-(2- t -Butylbenzoyloxy)benzenesulfonate; Sodium 4-
(4-decylbenzoyloxy)benzenesulfonate; sodium 4-(4-octadecylbenzoyloxy)benzenesulfonate; and mixtures thereof. The process of the invention is carried out by heating a mixture of the aryl ester and the alkali metal or alkaline earth metal salt of hydroxybenzenesulfonic acid in a suitable reaction vessel. Generally, this method operates from 200 to 350°C, more preferably from 250 to 350°C.
It is carried out at temperatures up to 325°C. Although not required, the process is preferably carried out under substantially anhydrous conditions, such that the components of the reaction system are combined and maintained under a substantially dry, inert atmosphere. However, some water present in the drug, e.g. hexane,
The chemicals used in the process can be removed from the chemicals by conventional techniques such as azeotropic distillation of the combined chemicals using organic solvents such as octane, toluene, xylene and the like. Yes, it is necessary to make it anhydrous before combining. Typically, oxygen-containing compounds other than the desired acyloxybenzene sulfonate salts can be produced by the method of the invention. Phenol and disodium phenol-2,4-disulfonate are the main by-products formed by the reaction.
However, as mentioned in the examples, the yield of acyloxybenzene sulfonate salt will be 90% by weight and higher. Removal of the phenol from the reaction mixture can be easily accomplished by distillation as soon as possible after it is formed.
Since the reaction is an equilibrium reaction, removal of the phenol helps drive the reaction to completion. There is generally no need to use a rectifier. However, if the aryl ester reactant used in the process has a boiling point approaching that of the phenol, the use of a rectification column is desirable. The relative proportions of reactants used in the reaction may be those required stoichiometrically, although other proportions may be used if desired. It is preferred to use an excess of aryl ester in the reaction since using more than the stoichiometric amount of ester also helps to drive the reaction to completion. Excellent results are obtained when the molar ratio of aryl ester to hydroxybenzenesulfonate salt is from 1.25 to 5:1. Typically, the reaction is carried out at ambient pressure, but pressures up to 1000 psig or more can be used if desired. The maximum pressure is only limited by the strength of the holding volume. However, when aryl esters having boiling points above approximately 350°C are used in the process of the present invention, the reaction can be carried out at reduced pressure to facilitate distillation of the by-product phenol. If desired, an inert liquid can be used as the reaction medium. However, the reaction can be carried out satisfactorily without the addition of any medium, especially if an excess of aryl ester reactant is used during the process. If a solvent is used, it is advantageous, although not necessary, that the solvent have a boiling point higher than the by-product phenol produced in this process and lower than the aryl ester reactant. In this way, it is possible to distill off substantially all of the unwanted phenol while preventing distillation of the allyl ester reactant during the reaction. This allows the distillation to be carried out at ambient pressure when high boiling aryl esters are used in the process, thus avoiding carrying out the reaction under reduced pressure which is necessary when no solvent is used. Examples of solvents that can be used in this process include chlorinated benzene, chlorinated toluene, high boiling alkanes such as undecane, tetradecane, hexadecane, mineral oil and high boiling straight and branched chain alkanes. In addition, triglyme, tetraglyme, 1,2
Aprotic solvents such as -diethoxyethane and amphoteric aprotic solvents such as N,N-dimethylacetamide, tetramethylene sulfone, N-methylpyrrolidone and similar materials can also be used. The acyloxybenzenesulfonate salt produced by this process is easily separated from the unreacted aryl ester and solvent remaining after removal of the by-product phenol. Preferably, the reaction mixture is filtered and the solid product is washed free of aryl ester and solvent by use of a low boiling solvent such as heptane, toluene, dichloromethane or diethyl ether. The low boiling solvent is then removed from the solid product by evaporation. Alternatively, the acyloxybenzenesulfonate salt product can be separated from the reaction mixture by dissolving it in the reaction solvent and water in which the aryl ester reactants are generally not soluble, and the organic and aqueous The phases are separated and the acyloxybenzenesulfonate salt is separated from the aqueous phase by known techniques such as crystallization or spray drying. The method of the invention will be further elucidated by the following illustrative examples. Example 1 Preparation of Phenyl Heptanoate Heptanoic acid (180.9 g: 1.39 mol), phenol were placed in a 2-stand, 3-neck round-bottomed flask equipped with an 8-inch Vigreux column equipped with a thermometer, magnetic stirrer, and Dean-Stark trap. (180.69g;
1.92 mol), toluene (216.5; 2.35 mol) and sulfuric acid (5.04 g; 0.0514 mol). The reaction mixture was heated to 131°C and held at this temperature for 5 hours to give 74% by weight of phenyl heptanoate. 0.08 mol of reaction product dissolved in 4.5 mol of water
Washed once with a solution of Na ₂ CO ₃ . The phase separation is approximately 20
Woke up a minute later. The organic layer was fractionally distilled at ambient pressure using a 20-plate Oldershaw column to remove phenol and toluene. The remaining liquid was then distilled through a 10-plate Oldershaw column at 50 Torr to yield 154.4 g of middle distillate.
(54% yield) of pure phenyl heptanoate. Example 2 Preparation of Sodium 4-Nonanoyloxybenzenesulfonate Sodium 4-hydroxybenzenesulfonate dihydrate (160 g , 0.670 mol), hexadecane (102 g), and octane (166 g).
The reaction mixture was refluxed until 15 ml of water collected in the trap. Then between the reaction flask and the trap
Combine a 16 mm x 300 mm Vigreux column and drain the trap intermittently over 1.5 hours to collect 100 ml.
Distillation continued until octane had been collected. Cool the flask slightly and use phenyl nonanoate (428.5
g; 1.38 mol) was added to the flask and removed by distillation. The resulting mixture was heated to a pot temperature of 292°C and between 180° and 282°C (180° and
Dean at overhead temperatures (including 282°C)
- Refluxed on Stark trap. The trap was occasionally drained to remove phenols. After 4 hours of reflux and 70 ml of phenol and approximately 60 ml of hexadecane were collected. At the end of the 4 hour period, the pot temperature was 301°C and the overhead temperature fluctuated between 275° and 282°C. The mixture was cooled and the solids were collected by filtration and washed on the filter with approximately 100 ml of octane. The filter cake was reslurried in approximately 400 ml of a mixture of hexane and diethyl ether, collected and then reslurried a second time in approximately 400 ml of a mixture of pentane and diethyl ether. The remaining solid was collected by vacuum filtration, washed with pentane and dried in an oven at 90°C to give 214.5g of a white solid. Analysis by cation titration revealed that the product was 86.9% by weight of sodium 4-
It was shown to consist of nonanoyloxybenzene sulfonate. Analysis by NMR shows that the product is also
It was shown to contain 2.8% by weight of disodium phenol-2,4 disulfonate with the remainder of the product consisting of sodium 4-hydroxybenzenesulfonate. Example 3 Preparation of Sodium 4-heptanoyloxybenzenesulfonate Sodium 4-heptanoyloxybenzene sulfonate was added to a 200 ml, 3-neck round bottom flask equipped with a 12 inch fractional distillation column equipped with a magnetic stirrer, thermocouple sheath, and Dean-Stark trap.
-Hydroxybenzenesulfonate dihydrate (19.5 g; 0.084 mol), phenyl heptanoate (47.6
g; 0.231 mol), 45 ml of octane and 20 ml of tetradecane. The reaction mixture was heated to reflux and the octane and water were removed by draining the trap. The reaction temperature reached 265°C after all the octane was removed. The reaction mixture was heated to a pot temperature of 265-267°C (overhead temperature 190-248°C).
for 2 hours and approximately 6.2 g of phenol was collected in the trap. Add 20 ml of tetradecane to the flask and add the reaction mixture.
It was heated to reflux for an additional 2.5 hours during which time an additional 3.6 g of phenol was collected. Refluxing was continued for an additional 2 hours during which time 20.5 g of tetradecane was collected. The reaction mixture was cooled and the solid was collected by vacuum filtration and washed three times with approximately 150 ml of diethyl ether each time. Analysis of the white product by cationic titration showed that it contained 88.2% by weight sodium 4-heptanoyloxybenzene sulfonate. A sample of the reaction product was refluxed with methanol and traces of sulfuric acid. When the resulting methyl ester was analyzed by VPC, the solid content was 3.01.
It was shown to contain milliequivalents (93% by weight) of sodium 4-heptanoyloxybenzenesulfonate. Similarly, several other experiments were performed with varying reactants, solvents, and reaction conditions. The results are given in the following table.

【table】

【table】

[Table] Eight
Rubenzene sulfone
(0.11)
mixture; 90%
Comparative Example 1 15g of sodium phenolsulfonate dihydrate (SPH・2H ₂ O) and caprylic acid (octanoic acid)
51 g were reacted using 0.15 g of p-toluenesulfonic acid catalyst in a mixture of 100 ml of decane and 50 ml of heptane. The SPH.2H ₂ O was first added to the alkane solvent and some of the heptane was distilled off to remove the water of hydrate. Other materials were added and the remainder of the heptane was added to the pot at a temperature of 185°C and at a head temperature of 170°C (n
- The boiling point of decane is 174°C). Dean
Refluxing was continued for 6 hours and 15 minutes while water was separated from the distillate using a Strk water separator. This resulted in a gray solid product. The gray solid product was analyzed by NMR to contain 75 mole percent sodium octanoyloxybenzene sulfonate and by titration to contain 75.2 weight percent of the desired product. These values are
It accurately represents the actual yield and is a valid value for comparison. Other undesirable amounts of disodium phenol disulfonate (approximately 4
%) produced. Comparative Example 2 The same reaction as in Comparative Example 1 was carried out in a mixture of heptane, decane and dodecane using a small amount of p-hydroxybenzenesulfonic acid as catalyst. The pot temperature was 210.7°C.The gray product was analyzed by NMR and titrated with 80% sodium octanoyloxybenzenesulfonate.
It was 74.1% by weight. The latter method is used as the standard method. Comparative Example 3 12.07 g in two stirred 300 ml necked flasks equipped with Vigreawx columns topped with Dean Stark water traps.
(0.052 mol) sodium phenol sulfonate dihydrate, 56 g nonylic acid and 50 ml heptane were added. Heptane was used to azeotropically dihydrate phenol fluoronate. The hydrocarbons are then boiled and removed to bring the flask temperature to
The temperature was adjusted to 242°C (169°C top) and the water was removed for 6 hours. cool the contents of the flask,
The solid (6.85 g) was then separated by filtration, washed with acetone, dried and analyzed for AOBS (acyloxybenzene sulfonate) content. The results of the two analyzes showed that 1.0 and 1.1% by weight of solids.
AOBS was confirmed. Example 4 The experiment of Comparative Example 1 was conducted using phenyl capreate instead of caprylic acid. As a result, the yield was 93% by weight using the titration method. Example 5 18.0 g of SPS.2H ₂ O was placed in a flask with 45 ml of octane and the mixture was distilled to remove the water of hydrate. Then add 68 g of 65% by weight phenyl nonaate (C ₉ acid) in cetane,
The mixture was heated to 294-297°C to distill off the phenol. Added more octane. The product was insoluble in alkanes and was collected by filtration, washed and dried. It was white or pale yellow in color and was 92.4% by weight sodium nonanoyloxybenzene sulfonate.

Claims (1)

Claims: 1. A process for preparing an alkali metal or alkaline earth metal salt of an acyloxybenzenesulfonate comprising reacting the corresponding hydroxybenzenesulfonate salt with an aryl ester at a temperature of about 200°C to 350°C. 2 The alkali metal or alkaline earth metal salt of the above acyloxybenzenesulfonate has the formula (wherein R is a hydrocarbyl group containing up to 30 carbon atoms selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl and M is an alkali metal or alkaline earth metal), The hydroxybenzenesulfonate salt of has the formula: And the above acyl ester has the formula 2. The method of claim 1, wherein R is as defined above. 3. The method of claim 2, wherein the compound having the general structure () is selected from sodium 4-heptanoyloxybenzenesulfonate; sodium 4-nonanoyloxybenzenesulfonate and mixtures thereof. 4 The molar ratio of aryl ester reactant to hydroxybenzenesulfonate salt reactant is 1.25 to 5:1
The method according to claim 2, which comprises: 5. A process according to claim 2, wherein said reaction is carried out in the presence of a solvent that is inert under the reaction conditions. 6 The solvent is decane, undecane, tetradecane,
A method according to claim 5, selected from hexadecane, mineral oil and mixtures thereof. 7. The method of claim 5, wherein said solvent is an aprotic solvent selected from triglyme, tetraglyme and 1,2-diethoxyethane. 8. The method of claim 5, wherein said solvent is an amphoteric aprotic solvent selected from N,N-dimethylacetamide, tetramethylene sulfone and N-methylpyrrolidinone.